Porous carbon-heteroatom-silicon inorganic/organic materials for chromatographic separations and process for the preparation thereof

ABSTRACT

The present invention provides porous carbon-heteroatom-silicon inorganic/organic homogenous copolymeric hybrid materials, methods for their preparation, and uses thereof, e.g., as chromatographic separations materials.

RELATED APPLICATION

This application is a Continuation of U.S. patent application Ser. No.12/446,871, filed Oct. 21, 2009, set to issue as U.S. Pat. No. 8,697,765on Apr. 15, 2014, which application is the U.S. national phase, pursuantto 35 U.S.C. §371, of PCT international application Ser. No.PCT/US2007/026246, filed Dec. 21, 2007, designating the United Statesand published in English on Jul. 17, 2008 as publication no. WO2008/085435 A1, which claims priority to U.S. provisional applicationSer. No. 60/880,339, filed Jan. 12, 2007. The entire contents of theaforementioned applications are incorporated herein by this reference.

BACKGROUND OF THE INVENTION

Packing materials for liquid chromatography (LC) are generallyclassified into two types: organic materials, e.g., polydivinylbenzene,and inorganic materials, e.g., silica.

As stationary phases for HPLC, silica-based materials result in columnsthat do not show evidence of shrinking or swelling and are mechanicallystrong. However, limited hydrolytic stability is a drawback withsilica-based columns, because silica may be readily dissolved underalkaline conditions, generally pH>8.0, leading to the subsequentcollapse of the chromatographic bed. Additionally, the bonded phase on asilica surface may be removed from the surface under acidic conditions,generally pH<2.0, and eluted off the column by the mobile phase, causingloss of analyte retention.

On the other hand, many organic materials are chemically stable againststrongly alkaline and strongly acidic mobile phases, allowingflexibility in the choice of mobile phase pH. However, organicchromatographic materials generally result in columns with lowefficiency, leading to inadequate separation performance, particularlywith low molecular-weight analytes. Furthermore, many organicchromatographic materials shrink and swell when the composition of themobile phase is changed. In addition, most organic chromatographicmaterials do not have the mechanical strength of typical chromatographicsilica.

In order to overcome the above-mentioned deficiencies while maintainingthe beneficial properties of purely organic and purely inorganicmaterials, others have attempted to simply mix organic and inorganicmaterials. For example, others have previously attempted to produce suchmaterials for optical sensors or gas separation membranes that aremixtures of organic polymers (e.g., poly(2-methyl-2-oxazoline),poly(N-vinylpyrrolidone), polystyrene, or poly(N,N-dimethylacrylamide)dispersed within silica. See, e.g., Chujo, Polymeric Materials: Science& Engineering, 84, 783 (2001); Tamaki, Polymer Bull., 39, 303 (1997);and Chujo, MRS Bull., 389 (May 2001). These materials, however, were notuseful for any liquid based separation application because they aretranslucent and non-porous. As a result, these materials lack capacityas a separation material.

Still others have attempted to make materials that have inorganic andorganic components covalently bound to each other. See, e.g., Feng, Q.,J. Mater. Chem. 10, 2490-94 (2000), Feng, Q., Polym. Preprints 41,515-16 (2000), Wei, Y., Adv. Mater. 12, 1448-50 (2000), Wei, Y. J.Polym. Sci. 18, 1-7 (2000). These materials, however, only contain verylow amounts of organic material, i.e., less than 1% C, and as a resultthey function essentially as inorganic silica gels.

Furthermore, these materials are non-porous until they are ground toirregular particles and then extracted to remove template porogenmolecules. Accordingly, it is not possible to make porous monolithicmaterials which have a useful capacity as a separation material.Irregularly-shaped particles are generally more difficult to pack thanspherical particles. It is also known that columns packed withirregularly-shaped particles generally exhibit poorer packed bedstability than spherical particles of the same size. The template agentsused in the synthesis of these materials are nonsurfactant opticallyactive compounds, and the use of such compounds limits the range ofporogen choices and increases their cost. The properties of thesematerials make them undesirable for use as LC packing materials.

SUMMARY OF THE INVENTION

The present invention provides a solution to the above-mentioneddeficiencies. In particular, the present invention provides a novelporous carbon-heteroatom-silicon hybrid inorganic/organic material forchromatographic separations, processes for its preparation, andseparations devices containing the chromatographic material. Thematerials of the invention incorporate a novel repeat unit, which isconnected to other repeat units by a carbon-heteroatom-silicon bond.Additionally, the materials of the invention have increased chemicalstability, increased mechanical stability, reduced swelling and reducedmicroporosity. Accordingly, the materials of the invention have avariety of uses. For example, the material of the invention may be usedas a liquid chromatography stationary phase; a sequestering reagent; asolid support for combinatorial chemistry; a solid support foroligosaccharide, polypeptide, or oligonucleotide synthesis; a solidsupport for a biological assay; a capillary biological assay device formass spectrometry; a template for a controlled large pore polymer film;a capillary chromatography stationary phase; an electrokinetic pumppacking material; a polymer additive; a catalyst; or a packing materialfor a microchip separation device.

Thus, in one aspect, the invention provides a porous inorganic/organichomogenous copolymeric hybrid material, comprising two or more repeatunits, wherein at least one repeat unit is an organosilane repeat unitD, wherein repeat unit D is selected from the group consisting of

wherein R₂ and R₄ are each independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl,C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl,or C₅-C₁₈ heteroaryl;

each R₇ or R₈ is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkenylene, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl,C₅-C₁₈ aryl, C₅-C₁₈ arylene, C₅-C₁₈ heteroaryl, or C₅-C₁₈ heteroarylene,wherein each of R₇ and R₈ may be optionally substituted;

X is O, NR_(A), or S(O)_(q);

R_(A) is C₁-C₆ alkyl, C₂-C₁₈ alkenyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈heterocycloalkyl, C₅-C₁₈ aryl, or C₅-C₁₈ heteroaryl; and

q is 0-2.

In one embodiment, the two or more repeat units are linked by at leastone carbon-heteroatom-silicon linker. In another embodiment, the porousinorganic/organic homogenous copolymeric hybrid material of theinvention has the formula(A)_(w)(B)_(x)(C)_(y)(D)_(z)wherein the order of repeat units A, B, C, and D may be random, block,or a combination of random and block and wherein:

A is an organic repeat unit which is covalently bonded to one or morerepeat units A, B, or D via an organic bond;

B is an organosiloxane repeat unit which is bonded to: one or morerepeat units A, B, or D via an organic bond; one or more repeat units B,C, or D via an inorganic bond; or one or more repeat units D via acarbon-heteroatom-silicon bond;

C is an inorganic repeat unit which is bonded to: one or more repeatunits B, C, or D via an inorganic bond; or one or more repeat units Dvia a carbon-heteroatom-silicon bond;

D is an organosilane repeat unit as defined in claim 1 and is bonded to:one or more repeat units A, B, or D via an organic bond; one or morerepeat units B, C, or D via an inorganic bond; or one or more repeatunits B, C, or D via a carbon-heteroatom-silicon bond;

-   -   w, x, and y are each independently positive numbers or zero,        wherein w+x+y>0; and    -   z is a positive number.        In a related embodiment, when w and x in the formula above are        0, the invention provides a material of the formula:        (C)_(y)(D)_(z)        wherein the order of repeat units C and D may be random, block,        or a combination of random and block;

C is an inorganic repeat unit which is bonded to: one or more repeatunits C or D via an inorganic bond; or one or more repeat units D via acarbon-heteroatom-silicon bond;

D is an organosilane repeat unit which is bonded to: one or more repeatunits C or D via an inorganic bond; one or more repeat units C or D viaa carbon-heteroatom-silicon bond; or one or more repeat units D via anorganic bond; and

y and z are positive numbers.

In certain embodiments, the materials of the invention may haveunreacted end groups, e.g., SiOH, Si(OH)₂, or Si(OH)₃, or unpolymerizedolefins.

Another aspect of the invention provides separation devices comprisingthe novel porous carbon-heteroatom-silicon hybrid inorganic/organicmaterials described herein.

Methods of preparation of such materials are contemplated by theinvention. Thus, in yet another aspect, the invention provides a methodof preparing a porous inorganic/organic homogenous copolymeric hybridmaterial comprising two or more repeat units, wherein at least onerepeat unit is an organosilane repeat unit D (previously described),comprising the steps of

(a) partially condensing an organic olefin, an alkenyl functionalizedsilane, an alkoxysilane, or a heterocyclic silane, or mixtures thereof,

(b) adding a heterocyclic silane, and

(c) further reacting the heterocyclic silane with the partiallycondensed polymer of step (a) to thereby prepare a porousinorganic/organic homogenous copolymeric hybrid material comprising acarbon-heteroatom-silicon functionality.

In a related aspect, the invention provides a method of preparing aporous inorganic/organic homogenous copolymeric hybrid materialcomprising two or more repeat units, wherein at least one repeat unit isan organosilane repeat unit D (previously described), comprising thesteps of

(a) preparing a polyoligomeric silaxane (POS) by partial condensation oftetraalkoxylsilane,

(b) adding a heterocyclic silane, and

(c) further reacting the heterocyclic silane with the POS to therebyprepare a porous inorganic/organic homogenous copolymeric hybridmaterial, comprising a carbon-heteroatom-silicon functionality.

In another related aspect, the invention provide a method of preparing aporous inorganic/organic homogenous copolymeric hybrid materialcomprising two or more repeat units, wherein at least one repeat unit isan organosilane repeat unit D (previously described), comprising thesteps of

(a) preparing a polyoligomeric silaxane (POS) by partial condensation oftetraalkoxylsilane,

(b) adding a heterocyclic silane, and

(c) further reacting the heterocyclic silane with the POS to therebyprepare a porous inorganic/organic homogenous copolymeric hybridmaterial, comprising a carbon-heteroatom-silicon functionality; whereinthe heterocyclic silane is selected from the group consisting of

wherein

each R is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl,C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, C₆-C₁₈ aralkyl, C₆-C₁₈ heteroaralkyl, —Si(R^(c))₄,—C(O)R^(c), —C(S)R^(c), —C(NR)R^(c), —S(O)R^(c), —S(O)₂R^(c),—P(O)R^(c)R^(c), or —P(S)R^(c)R^(c);

each R^(c) is independently, H, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, —OC₁-C₁₈ alkyl; —OC₅-C₁₈ aryl; —OC₃-C₁₈ heterocycloalkyl,—OC₅-C₁₈ heteroaryl, —NHC₁-C₁₈ alkyl; or —N(C₁-C₁₈ alkyl)₂;

R₂ and R₄ are each independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, orC₅-C₁₈ heteroaryl;

each R₇ or R₈ is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkenylene, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl,C₅-C₁₈ aryl, C₅-C₁₈ arylene, C₅-C₁₈ heteroaryl, or C₅-C₁₈ heteroarylene,wherein each of R₇ and R₈ may be optionally substituted;

X is O, NR_(A), or S(O)_(q);

R_(A) is C₁-C₆ alkyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈aryl, or C₅-C₁₈ heteroaryl; and

q is 0-2.

In another aspect, the invention provides a method of preparing a porousinorganic/organic homogenous copolymeric hybrid material of the formula:(A)_(w)(B)_(x)(C)_(y)(D)_(z)wherein the order of repeat units A, B, C, and D may be random, block,or a combination of random and block; and wherein

A is an organic repeat unit which is covalently bonded to one or morerepeat units A, B, or D via an organic bond;

B is an organosiloxane repeat unit which is bonded to: one or morerepeat units A, B, or D via an organic bond; one or more repeat units B,C, or D via an inorganic bond; or one or more repeat unit D via acarbon-heteroatom-silicon bond;

C is an inorganic repeat unit which is bonded to: one or more repeatunits B, C, or D via an inorganic bond; or one or more repeat unit D viaa carbon-heteroatom-silicon bond;

D is an organosilane repeat unit which is bonded to one or more repeatunits A, B, or D via an organic bond; bonded to one or more repeat unitsB, C, or D via an inorganic bond; or one or more repeat units B, C, or Dvia a carbon-heteroatom-silicon bond;

w, x, and y are positive numbers or zero; wherein w+x+y>0, z is apositive number;

the method comprising the steps of

(a) partially condensing an organic olefin, an alkenyl functionalizedsilane, an alkoxysilane, or a heterocyclic silane, or mixtures thereof,

(b) adding a heterocyclic silane, and

(c) further reacting the heterocyclic silane with the partiallycondensed polymer of step (a) to thereby prepare a porousinorganic/organic homogenous copolymeric hybrid material comprising acarbon-heteroatom-silicon functionality.

In yet another aspect, the invention provides a method of preparing aporous inorganic/organic homogenous copolymeric hybrid material of theformula:(C)_(y)(D)_(z)wherein the order of repeat units C and D may be random, block, or acombination of random and block; and wherein

C is an inorganic repeat unit which is bonded to: one or more repeatunits C or D via an inorganic bond; or one or more repeat units D via acarbon-heteroatom-silicon bond;

D is an organosilane repeat unit which is bonded to: one or more repeatunits C or D via an inorganic bond; one or more repeat units C or D viaa carbon-heteroatom-silicon bond; or one or more repeat units D via anorganic bond, and

y and z are positive numbers;

the method comprising the steps of

(a) preparing a polyoligomeric silaxane (POS) by partial condensation ofa tetraalkoxylsilane,

(b) adding a heterocyclic silane, and

(c) further reacting the heterocyclic silane with the PUS to therebyprepare a porous inorganic/organic homogenous copolymeric hybridmaterial, comprising a carbon-heteroatom-silicon functionality.

Other aspects, embodiments and features of the invention will becomeapparent form the following detailed description of the invention.

DETAILED DESCRIPTION OF THE INVENTION Definitions

The present invention will be more fully illustrated by reference to thedefinitions set forth below.

As used herein, the term “porous inorganic/organic homogenouscopolymeric hybrid material” includes materials comprising inorganicrepeat units (e.g., comprising O—Si—O bonds between repeat units),organic repeat units (e.g., comprising C—C bonds between repeat units),and mixed organic-inorganic repeat units (e.g., comprising both C—C andO—Si—O bonds between repeat units).

The term “porous” indicates that the microscopic structure of thematerial contains pores of a measurable volume, so that the materialscan be used, for example, as solid supports in chromatography.

The term “inorganic/organic copolymeric hybrid” indicates that thematerial comprises a copolymer of organic, inorganic, and mixedorganic/inorganic repeat units.

The term “homogenous” indicates that the structure of the material atthe chemical level is substantially interconnected via chemical bonds,as opposed to the prior art materials that simply comprise mixtures ofdiscrete organic and inorganic materials.

The term “hybrid” refers to a material having chemical bonds amonginorganic and organic repeat units of a composite material therebyforming a matrix throughout the material itself, as opposed to a mixtureof discrete chemical compounds.

Polyorganoalkoxysiloxane (POS) and polyalkylalkoxysiloxane (PAS) arelarge molecules, either linear or preferably three-dimensional networks,that are formed by the condensation of silanols, where the silanols areformed, e.g., by hydrolysis of halo- or alkoxy-substituted silanes.

As used herein, the term “protecting group” means a protected functionalgroup which may be intended to include chemical moieties that shield afunctional group from chemical reaction or interaction such that uponlater removal (“deprotection”) of the protecting group, the functionalgroup can be revealed and subjected to further chemistry. The term alsoincludes a functional group which that does not interfere with thevarious polymerization and condensation reactions used in the synthesisof the materials of the invention, but which that may be converted aftersynthesis of the material into a functional group that may itself befurther derivatized. For example, an organic monomer reagent A maycontain an aromatic nitro group which that would not interfere with thepolymerization or condensation reactions. However, after thesepolymerization and condensation reactions have been carried out, thenitro group may be reduced to an amino group (e.g., an aniline), whichitself may then be subjected to further derivatization by a variety ofmeans known in the art. In this manner, additional functional groups maybe incorporated into the material after the syntheses of the materialitself. See generally, Greene, T. W. and Wuts, P. G. M. “ProtectiveGroups in Organic Synthesis,” Second Edition, Wiley, 1991. In somecases, preferable protecting group strategies do not involve the use ofheavy metals (e.g., transition metals) in the protection or deprotectionstep as these metals may be difficult to remove from the materialcompletely.

The porous inorganic/organic homogenous copolymeric hybrid particles andmaterials possess both organic groups and silanol groups which mayadditionally be substituted or derivatized with a surface modifier.“Surface modifiers” include (typically) organic groups which impart acertain chromatographic functionality to a chromatographic stationaryphase. Surface modifiers such as disclosed herein are attached to thebase material, e.g., via derivatization or coating and latercrosslinking, imparting the chemical character of the surface modifierto the base material. In one embodiment, the organic groups of thehybrid materials react to form an organic covalent bond with a surfacemodifier. The modifiers may form an organic covalent bond to thematerial's organic group via a number of mechanisms well known inorganic and polymer chemistry including, but not limited to,nucleophilic, electrophilic, cycloaddition, free-radical, carbene,nitrene, and carbocation reactions. Organic covalent bonds are definedto involve the formation of a covalent bond between the common elementsof organic chemistry including, but not limited to, hydrogen, boron,carbon, nitrogen, oxygen, silicon, phosphorus, sulfur, and the halogens.In addition, carbon-silicon and carbon-oxygen-silicon bonds are definedas organic covalent bonds, whereas silicon-oxygen-silicon bonds are notdefined as organic covalent bonds. In general, the porousinorganic/organic homogenous copolymeric hybrid particles may bemodified by an organic group surface modifier, a silanol group surfacemodifier, a polymeric coating surface modifier, and combinations of theaforementioned surface modifiers.

The term “aliphatic group” includes organic compounds characterized bystraight or branched chains, typically having between 1 and 22 carbonatoms. Aliphatic groups include alkyl groups, alkenyl groups and alkynylgroups. In complex structures, the chains may be branched orcross-linked.

Alkyl groups include saturated hydrocarbons having one or more carbonatoms, including straight-chain alkyl groups and branched-chain alkylgroups. Such hydrocarbon moieties may be substituted on one or morecarbons with, for example, a halogen, a hydroxyl, a thiol, an amino, analkoxy, an alkylcarboxy, an alkylthio, or a nitro group. Unless thenumber of carbons is otherwise specified, “lower aliphatic” as usedherein means an aliphatic group, as defined above (e.g., lower alkyl,lower alkenyl, lower alkynyl), but having from one to six carbon atoms.Representative of such lower aliphatic groups, e.g., lower alkyl groups,are methyl, ethyl, n-propyl, isopropyl, 2-chloropropyl, n-butyl,sec-butyl, 2-aminobutyl, isobutyl, tert-butyl, 3-thiopentyl, and thelike.

As used herein, the term “nitro” means —NO₂; the term “halogen”designates —F, —Cl, —Br or —I; the term “thiol” means SH; and the term“hydroxyl” means —OH. Thus, the term “alkylamino” as used herein meansan alkyl group, as defined above, having an amino group attachedthereto. Suitable alkylamino groups include groups having 1 to about 12carbon atoms, preferably from 1 to about 6 carbon atoms.

The term “alkylthio” refers to an alkyl group, as defined above, havinga sulfhydryl group attached thereto. Suitable alkylthio groups includegroups having 1 to about 12 carbon atoms, preferably from 1 to about 6carbon atoms.

The term “alkylcarboxyl” as used herein means an alkyl group, as definedabove, having a carboxyl group attached thereto.

The term “alkoxy” as used herein means an alkyl group, as defined above,having an oxygen atom attached thereto. Representative alkoxy groupsinclude groups having 1 to about 12 carbon atoms, preferably 1 to about6 carbon atoms, e.g., methoxy, ethoxy, propoxy, tert-butoxy and thelike.

The terms “alkenyl” and “alkynyl” refer to unsaturated aliphatic groupsanalogous to alkyls, but which contain at least one double or triplebond respectively. Suitable alkenyl and alkynyl groups include groupshaving 2 to about 12 carbon atoms, preferably from 1 to about 6 carbonatoms.

The term “alicyclic group” or “cycloalkyl” includes closed ringstructures of three or more carbon atoms. Such groups includecycloparaffins or naphthenes which are saturated cyclic hydrocarbons,cycloolefins which are unsaturated with two or more double bonds, andcycloacetylenes which have a triple bond. They do not include aromaticgroups. Examples of cycloparaffins include cyclopropane, cyclohexane,and cyclopentane. Examples of cycloolefins include cyclopentadiene andcyclooctatetraene. Alicyclic groups also include fused ring structuresand substituted alicyclic groups such as alkyl substituted alicyclicgroups. In the instance of the alicyclics such substituents may furthercomprise a lower alkyl, a lower alkenyl, a lower alkoxy, a loweralkylthio, a lower alkylamino, a lower alkylcarboxyl, a nitro, ahydroxyl, —CF₃, —CN, or the like.

The term “heterocyclic group” includes closed ring structures in whichone or more of the atoms in the ring is an element other than carbon,for example, nitrogen, sulfur, or oxygen. Heterocyclic groups may besaturated or unsaturated and heterocyclic groups, herein includingheterocycloalkyl, heteroaromatic, or heteroalicyclic, such as pyrroleand furan may have aromatic character. They include fused ringstructures such as quinoline and isoquinoline. Other examples ofheterocyclic groups include pyridine and purine. Heterocyclic groups mayalso be substituted at one or more constituent atoms with, for example,a halogen, a lower alkyl, a lower alkenyl, a lower alkoxy, a loweralkylthio, a lower alkylamino, a lower alkylcarboxyl, a nitro, ahydroxyl, —CF₃, —CN, or the like. Suitable heteroaromatic,heterocycloalkyl, and heteroalicyclic groups generally will have 1 to 3separate or fused rings with 3 to about 8 members per ring and one ormore N, O or S atoms, e.g., coumarinyl, quinolinyl, pyridyl, pyrazinyl,pyrimidyl, furyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl,indolyl, benzofuranyl, benzothiazolyl, tetrahydrofuranyl,tetrahydropyranyl, piperidinyl, morpholino and pyrrolidinyl.

The term “aromatic group” or “aryl” includes unsaturated cyclichydrocarbons containing one or more rings. Aromatic groups include 5-and 6-membered single-ring groups which may include from zero to fourheteroatoms, for example, benzene, pyrrole, furan, thiophene, imidazole,oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine, pyridazineand pyrimidine, and the like. The aromatic ring may be substituted atone or more ring positions with, for example, a halogen, a lower alkyl,a lower alkenyl, a lower alkoxy, a lower alkylthio, a lower alkylamino,a lower alkylcarboxyl, a nitro, a hydroxyl, —CF₃, —CN, or the like.

The term “alkyl” includes saturated aliphatic groups, includingstraight-chain alkyl groups, branched-chain alkyl groups, cycloalkyl(alicyclic) groups, alkyl substituted cycloalkyl groups, and cycloalkylsubstituted alkyl groups. In certain embodiments, a straight chain orbranched chain alkyl has 30 or fewer carbon atoms in its backbone, e.g.,C₁-C₃₀ for straight chain or C₃-C₃₀ for branched chain. In certainembodiments, a straight chain or branched chain alkyl has 20 or fewercarbon atoms in its backbone, e.g., C₁-C₂₀ for straight chain or C₃-C₂₀for branched chain, and more preferably 18 or fewer. Likewise, preferredcycloalkyls have from 4-10 carbon atoms in their ring structure, andmore preferably have 4-7 carbon atoms in the ring structure.

The term “lower alkyl” refers to alkyl groups having from 1 to 6 carbonsin the chain, and to cycloalkyls having from 3 to 6 carbons in the ringstructure.

Moreover, the term “alkyl” (including “lower alkyl”) as used throughoutthe specification and claims includes both “unsubstituted alkyls” and“substituted alkyls,” the latter of which refers to alkyl moietieshaving substituents replacing a hydrogen on one or more carbons of thehydrocarbon backbone. Such substituents may include, for example,halogen, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy,aryloxycarbonyloxy, carboxylate, alkylcarbonyl, alkoxycarbonyl,aminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato,phosphinato, cyano, amino (including alkyl amino, dialkylamino,arylamino, diarylamino, and alkylarylamino), acylamino (includingalkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), amidino,imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfate,sulfonato, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido,heterocyclyl, aralkyl, or an aromatic or heteroaromatic moiety. It willbe understood by those skilled in the art that the moieties substitutedon the hydrocarbon chain may themselves be substituted, if appropriate.Cycloalkyls may be further substituted, e.g., with the substituentsdescribed above.

An “aralkyl” moiety is an alkyl substituted with an aryl, e.g., having 1to 3 separate or fused rings and from 6 to about 18 carbon ring atoms,e.g., phenylmethyl (benzyl). A “heteroaralkyl moiety herein refers to aheteroalkyl substituted with an aryl, or an alkyl substituted with aheteroaryl group.

The term “aryl” includes 5- and 6-membered single-ring aromatic groupsthat may include from zero to four heteroatoms, for example,unsubstituted or substituted benzene, pyrrole, furan, thiophene,imidazole, oxazole, thiazole, triazole, pyrazole, pyridine, pyrazine,pyridazine and pyrimidine, and the like. Aryl groups also includepolycyclic fused aromatic groups such as naphthyl, quinolyl, indolyl,and the like. The aromatic ring may be substituted at one or more ringpositions with such substituents, e.g., as described above for alkylgroups. Suitable aryl groups include unsubstituted and substitutedphenyl groups.

The term “aryloxy” as used herein means an aryl group, as defined above,having an oxygen atom attached thereto.

The term “aralkoxy” as used herein means an aralkyl group, as definedabove, having an oxygen atom attached thereto. Suitable aralkoxy groupshave 1 to 3 separate or fused rings and from 6 to about 18 carbon ringatoms, e.g., O-benzyl.

The term “amino,” as used herein, refers to an unsubstituted orsubstituted moiety of the formula —NR_(a)R_(b), in which R_(a) and R_(b)are each independently hydrogen, alkyl, aryl, or heterocyclyl, or R_(a)and R_(b), taken together with the nitrogen atom to which they areattached, form a cyclic moiety having from 3 to 8 atoms in the ring.Thus, the term “amino” includes cyclic amino moieties such aspiperidinyl or pyrrolidinyl groups, unless otherwise stated. An“amino-substituted amino group” refers to an amino group in which atleast one of R_(a) and R_(b), is further substituted with an aminogroup.

The terms alkylene, alkeneylene, alkynylene, arylene, heteroarylene,cycloalkylene, and so forth herein refer to groups that are divalent andsubstituted with at least two additional substituents, e.g., arylenerefers to a disubstituted aryl ring.

The term “porogen” refers to a pore forming material, that is a chemicalmaterial dispersed in a material as it is formed that is subsequentlyremoved to yield pores or voids in the material.

The term “end capping” a chemical reaction step in which a resin thathas already been synthesized, but that may have residual unreactedgroups (e.g., silanol groups in the case of a silicon-based inorganicresin) are passivated by reaction with a suitable reagent. For example,again in the case of silicon-based inorganic resins, such silanol groupsmay be methylated with a methylating reagent such ashexamethyldisilazane.

Hybrid Materials of the Invention

In certain aspects, the invention provides a porous inorganic/organichomogenous copolymeric hybrid material, comprising two or more repeatunits, wherein at least one repeat unit is an organosilane repeat unitD, selected from the group consisting of

wherein R₂ and R₄ are each independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl,C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl,or C₅-C₁₈ heteroaryl;

each R₇ or R₈ is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkenylene, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl,C₅-C₁₈ aryl, C₅-C₁₈ arylene, C₅-C₁₈ heteroaryl, or C₅-C₁₈ heteroarylene,wherein each of R₇ and R₈ may be optionally substituted;

X is O, NR_(A), or S(O)_(q);

R_(A) is C₁-C₆ alkyl, C₂-C₁₈ alkenyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈heterocycloalkyl, C₅-C₁₈ aryl, or C₅-C₁₈ heteroaryl; and

q is 0-2.

In one embodiment, the two or more repeat units are linked by at leastone carbon-heteroatom-silicon linker. In a further embodiment, theheteroatom in the carbon-heteroatom-silicon linker is selected from O,N, or S.

In another embodiment, the invention provides a porous inorganic/organichomogenous copolymeric hybrid material of formula I(A)_(w)(B)_(x)(C)_(y)(D)_(z);  (Formula I)wherein the order of repeat units A, B, C, and D may be random, block,or a combination of random and block and wherein:

A is an organic repeat unit which is covalently bonded to one or morerepeat units A, B, or D via an organic bond;

B is an organosiloxane repeat unit which is bonded to: one or morerepeat units A, B, or D via an organic bond; one or more repeat units B,C, or D via an inorganic bond; or one or more repeat unit D via acarbon-heteroatom-silicon bond;

C is an inorganic repeat unit which is bonded to: one or more repeatunits B, C, or D via an inorganic bond; or one or more repeat unit D viaa carbon-heteroatom-silicon bond;

D is an organosilane repeat unit as defined above and is bonded to: oneor more repeat units A, B, or D via an organic bond; one or more repeatunits B, C, or D via an inorganic bond; or one or more repeat units B,C, or D via a carbon-heteroatom-silicon bond;

-   -   w, x, and y are each independently positive numbers or zero,        wherein w+x+y>0; and z is a positive number.

In yet another embodiment, the invention provides a porousinorganic/organic homogenous copolymeric hybrid material of Formula II,which is a material of Formula I, wherein w and x are 0, providing amaterial of formula II:(C)_(y)(D)_(z);  (Formula II)wherein the order of repeat units C and D may be random, block, or acombination of random and block;

C is an inorganic repeat unit which is bonded to: one or more repeatunits C or D via an inorganic bond; or one or more repeat units D via acarbon-heteroatom-silicon bond;

D is an organosilane repeat unit as defined above, which is bonded to:one or more repeat units C or D via an inorganic bond; one or morerepeat units C or D via a carbon-heteroatom-silicon bond; or one or morerepeat units D via an organic bond; and y and z are positive numbers.

In certain embodiments, the invention provides a material wherein D isbonded to one or more repeat units of B, C, or D via acarbon-heteroatom-silicon bond. In other embodiments, D is bonded to oneor more repeat units of B, C, or D via a carbosiloxane bond (C—O—Si).

The invention also embodies the material above, wherein the silicon atomof the group D monomer is attached to the heteroatom of thecarbon-heteroatom-silicon linker.

In another embodiment, the invention provides a material, wherein thesilicon atom of the group D monomer is attached to a carbon atom.

In still another embodiment, the invention provides a material, whereinthe carbon-heteroatom-silicon functionality is incorporated into thematerial via a ring opening reaction of a heterocyclic silane compound.In one embodiment, the heterocyclic silane is selected from the groupconsisting of

wherein

each R is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl,C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, C₆-C₁₈ aralkyl, C₆-C₁₈ heteroaralkyl, —Si(R^(c))₄,—C(O)R^(c), —C(S)R^(c), —C(NR)R^(c), —S(O)R^(c), —S(O)₂R^(c),—P(O)R^(c)R^(c), or —P(S)R^(c)R^(c);

each R^(c) is independently, H, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, —OC₁-C₁₈ alkyl; —OC₅-C₁₈ aryl; —OC₃-C₁₈ heterocycloalkyl,—OC₅-C₁₈ heteroaryl, —NHC₁-C₁₈ alkyl; or —N(C₁-C₁₈ alkyl)₂;

R₂ and R₄ are each independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, orC₅-C₁₈ heteroaryl;

each R₇ or R₈ is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkenylene, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl,C₅-C₁₈ aryl, C₅-C₁₈ arylene, C₅-C₁₈ heteroaryl, or C₅-C₁₈ heteroarylene,wherein each of R₇ and R₈ may be optionally substituted;

X is O, NR_(A), or S(O)_(q);

R_(A) is C₁-C₆ alkyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈aryl, or C₅-C₁₈ heteroaryl; and q is 0-2.

In certain embodiments, the invention provides a material of formula I,wherein A is a substituted ethylene group, B is a oxysilyl-substitutedalkylene group, C is a oxysilyl group, and D is a silyl group.

Repeat Units

Repeat unit “A” may be derived from a variety of organic monomerreagents possessing one or more polymerizable moieties, capable ofundergoing polymerization, e.g., a free radical-mediated polymerization.“A” monomers may be oligomerized or polymerized by a number of processesand mechanisms including, but not limited to, chain addition and stepcondensation processes, radical, anionic, cationic, ring-opening, grouptransfer, metathesis, and photochemical mechanisms. In one embodiment, Ais selected from the group consisting of

wherein

each R is independently H or a C₁-C₁₀ alkyl group;

k is an integer from 3-6;

m is an integer of from 1 to 20;

n is an integer of from 0 to 10; and

Q is hydrogen, N(C₁₋₆alkyl)₃, N(C₁₋₆ alkyl)₂ (C₁₋₆alkylene-SO₃), orC(C₁₋₆hydroxy alkyl)₃.

In a further embodiment of repeat unit A, each R is independentlyhydrogen, methyl, ethyl, or propyl.

Repeat unit “B” may be derived from several mixed organic-inorganicmonomer reagents possessing two or more different polymerizablemoieties, capable of undergoing polymerization, e.g., a freeradical-mediated (organic) and hydrolytic (inorganic) polymerization.Such “B” repeat units are organosiloxanes. “B” monomers may beoligomerized or polymerized by a number of processes and mechanismsincluding, but not limited to, chain addition and step condensationprocesses, radical, anionic, cationic, ring-opening, group transfer,metathesis, and photochemical mechanisms. In another embodiment, theinvention provides a material of formula I, wherein B is selected fromthe group consisting of

Repeat unit “C” may be an inorganic repeat unit. In one embodiment, theinvention provides a material, wherein C is

Repeat unit “D” may be an organosilane, derived from a heterocyclicsilane, and is selected from the group consisting of

wherein R₂ and R₄ are each independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl,C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl,or C₅-C₁₈ heteroaryl;

each R₇ or R₈ is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkenylene, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl,C₅-C₁₈ aryl, C₅-C₁₈ arylene, C₅-C₁₈ heteroaryl, or C₅-C₁₈ heteroarylene,wherein each of R₇ and R₈ may be optionally substituted;

X is O, NR_(A), or S(O)_(q);

R_(A) is C₁-C₆ alkyl, C₂-C₁₈ alkenyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈heterocycloalkyl, C₅-C₁₃ aryl, or C₅-C₁₈ heteroaryl; and q is 0-2.

Bonds

In one embodiment, the invention provides a material wherein organicbonds are formed via chain addition. In a further embodiment, theorganic bonds are formed between an organic olefin monomer and analkenyl-functionalized silane monomer. In another further embodiment,the organic bonds are formed between an organic olefin monomer and anorganic olefin monomer. In still another further embodiment, the organicbonds are formed between an organic olefin monomer and a heterocyclicsilane monomer.

In other embodiments, the invention provides a material wherein theorganic bonds are formed between an alkenyl-functionalized silanemonomer and an alkenyl-functionalized silane monomer. In a furtherembodiment, the organic bonds are formed between analkenyl-functionalized silane monomer and a heterocyclic silane monomer.In another further embodiment, the organic bonds are formed between aheterocyclic silane monomer and a heterocyclic silane monomer.

In certain embodiments, the invention provides a material whereininorganic bonds are formed via step condensation. In a furtherembodiment, the inorganic bonds are formed between analkenyl-functionalized silane monomer and an alkoxy silane monomer. Inanother further embodiment, the inorganic bonds are formed between analkenyl-functionalized silane monomer and an alkenyl-functionalizedsilane monomer. In other embodiments, the inorganic bonds are formedbetween an alkenyl-functionalized silane monomer and a heterocyclicsilane monomer. In still another embodiment, the inorganic bonds areformed between an alkoxy silane monomer and an alkoxy silane monomer. Inyet another embodiment, the inorganic bonds are formed between an alkoxysilane monomer and a heterocyclic silane monomer. In other embodiments,the inorganic bonds are formed between a heterocyclic silane monomer anda heterocyclic silane monomer.

In another embodiment, the invention provides a material whereincarbon-heteroatom-silicon bonds are formed via ring opening. In afurther embodiment, the ring opening bonds are formed between analkenyl-functionalized silane monomer and a heterocyclic silane monomer.In another further embodiment, the ring opening bonds are formed betweenan alkoxy silane monomer and a heterocyclic silane monomer. In stillanother further embodiment, the ring opening bonds are formed between aheterocyclic silane monomer and a heterocyclic silane monomer.

Monomers

In certain embodiments, the invention provides a porousinorganic/organic homogenous copolymeric hybrid material, comprisingorganic bonds formed between an organic olefin monomer and aheterocyclic silane monomer, wherein the organic olefin monomer isselected from the group consisting of divinylbenzene, styrene,vinylbenzylchloride, ethylene glycol dimethacrylate,1-vinyl-2-pyrrolidinone, N-vinylcaprolactam, tert-butylmethacrylate,acrylamide, methacrylamide, N,N′-(1,2-dihydroxyethylene)bisacrylamide,N,N′-ethylenebisacrylamide, N,N′-methylenebisacrylamide, butyl acrylate,ethyl acrylate, methyl acrylate, 2-(acryloxy)-2-hydroxypropylmethacrylate, 3-(acryloxy)-2-hydroxypropyl methacrylate,trimethylolpropane triacrylate, trimethylolpropane ethoxylatetriacrylate, tris[(2-acryloyloxy)ethyl]isocyanurate, acrylonitrile,methacrylonitrile, itaconic acid, methacrylic acid,trimethylsilylmethacrylate, N-[tris(hydroxymethyl) methyl]acrylamide,(3-acrylamidopropyl)trimethylammonium chloride,[3-(methacryloylamino)propyl]dimethyl(3-sulfopropyl)ammonium hydroxideinner salt,

and the heterocyclic silane is selected from group consisting of:

wherein

each R is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl,C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, C₆-C₁₈ aralkyl, C₆-C₁₈ heteroaralkyl, —Si(R^(c))₄,—C(O)R^(c), —C(S)R^(c), —C(NR)R^(c), —S(O)R^(c), —S(O)₂R^(c),—P(O)R^(c)R^(c), or —P(S)R^(c)R^(c);

each R^(c) is independently, H, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, —OC₁-C₁₈ alkyl; —OC₅-C₁₈ aryl; —OC₃-C₁₈ heterocycloalkyl,—OC₅-C₁₈ heteroaryl, —NHC₁-C₁₈ alkyl; or —N(C₁-C₁₈ alkyl)₂;

R₂ and R₄ are each independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, orC₅-C₁₈ heteroaryl;

each R₇ or R₈ is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₅alkenylene, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl,C₅-C₁₈ aryl, C₅-C₁₈ arylene, C₅-C₁₈ heteroaryl, or C₅-C₁₈ heteroarylene,wherein each of R₇ and R₈ may be optionally substituted;

X is O, NR_(A), or S(O)_(q);

R_(A) is C₁-C₆ alkyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈aryl, or C₅-C₁₈ heteroaryl; and q is 0-2.

In another embodiment, the invention provides a porous inorganic/organichomogenous copolymeric hybrid material, comprising organic bonds formedbetween an alkenyl-functionalized silane monomer and a heterocyclicsilane monomer, wherein the alkenyl-functionalized silane monomer isselected from the group consisting of methacryloxypropyltrimethoxysilane, methacryloxypropyl triethoxysilane,vinyltriethoxysilane, vinyltrimethoxysilane,N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyl triethoxysilane,(3-acryloxypropyl)trimethoxysilane,O-(methacryloxyethyl)-N-(triethoxysilylpropyl)urethane,N-(3-methacryloxy-2-hydroxypropyl)-3-aminopropyl triethoxysilane,methacryloxy methyltriethoxysilane, methacryloxymethyl trimethoxysilane,methacryloxypropy methyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryl oxypropyltris (methoxyethoxy)silane,3-(N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilanehydrochloride,

wherein

each R is independently H or a C₁-C₁₀ alkyl group and wherein R′ isindependently H or a C₁-C₁₀ alkyl group;

and the heterocyclic silane is selected from group consisting of

wherein

each R is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl,C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, C₆-C₁₈ aralkyl, C₆-C₁₈ heteroaralkyl, —Si(R^(c))₄,—C(O)R^(c), —C(S)R^(c), —C(NR)R^(c), —S(O)R^(c), —S(O)₂R^(c),—P(O)R^(c)R^(c), or —P(S)R^(c)R^(c);

each R^(c) is independently, H, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, —OC₁-C₁₈ alkyl; —OC₅-C₁₈ aryl; —OC₃-C₁₈ heterocycloalkyl,—OC₅-C₁₈ heteroaryl, —NHC₁-C₁₈ alkyl; or —N(C₁-C₁₈ alkyl)₂;

R₂ and R₄ are each independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, orC₅-C₁₈ heteroaryl;

each R₇ or R₈ is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkenylene, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl,C₅-C₁₈ aryl, C₅-C₁₈ arylene, C₅-C₁₈ heteroaryl, or C₅-C₁₈ heteroarylene,wherein each of R₇ and R₈ may be optionally substituted;

X is O, NR_(A), or S(O)_(q);

R_(A) is C₁-C₆ alkyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈aryl, or C₅-C₁₈ heteroaryl; and q is 0-2.

In another embodiment, the invention provides a porous inorganic/organichomogenous copolymeric hybrid material, comprising heterocyclic silanemonomers, wherein each heterocyclic silane monomer is independentlyselected from the group consisting of

wherein

each R is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl,C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, C₆-C₁₈ aralkyl, C₆-C₁₈ heteroaralkyl, —C(O)R^(c),—C(S)R^(c), —C(NR)R^(c), —S(O)R^(c), —S(O)₂R^(c), —P(O)R^(c)R^(c), or—P(S)R^(c)R^(c);

each R^(c) is independently, H, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, —OC₁-C₁₈ alkyl; —OC₅-C₁₈ aryl; —OC₃-C₁₈ heterocycloalkyl,—OC₅-C₁₈ heteroaryl, —NHC₁-C₁₈ alkyl; or —N(C₁-C₁₈ alkyl)₂;

R₂ and R₄ are each independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, orC₅-C₁₈ heteroaryl;

each R₇ or R₈ is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkenylene, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl,C₅-C₁₈ aryl, C₅-C₁₈ arylene, C₅-C₁₈ heteroaryl, or C₅-C₁₈ heteroarylene,wherein each of R₇ and R₈ may be optionally substituted;

X is O, NR_(A), or S(O)_(q);

R_(A) is C₁-C₆ alkyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈aryl, or C₅-C₁₈ heteroaryl; and q is 0-2.

In another embodiment, the invention provides a porous inorganic/organichomogenous copolymeric hybrid material, comprising analkenyl-functionalized silane monomer and a heterocyclic silane monomer,wherein the alkenyl-functionalized silane monomer is selected from thegroup consisting of methacryloxypropyl trimethoxysilane,methacryloxypropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane,(3-acryloxypropyl)trimethoxysilane,O-(methacryloxyethyl)-N-(triethoxysilylpropyl)urethane, N-(3-methacryloxy-2-hydroxypropyl)-3-aminopropyltricthoxysilane,methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane,methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane,methacryloxypropyltris(methoxyethoxy)silane,3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilanehydrochloride,

wherein

each R is independently H or a C₁-C₁₀ alkyl group and wherein R′ isindependently H or a C₁-C₁₀ alkyl group; and the heterocyclic silane isselected from group consisting of

wherein

each R is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl,C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, C₆-C₁₈ aralkyl, C₆-C₁₈ heteroaralkyl, —Si(R^(c))₄,—C(O)R^(c), —C(S)R^(c), —C(NR)R^(c), —S(O)R^(c), —S(O)₂R′,—P(O)R^(c)R^(c), or —P(S)R^(c)R^(c);

each R^(c) is independently, H, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, —OC₁-C₁₈ alkyl; —OC₅-C₁₈ aryl; —OC₃-C₁₈ heterocycloalkyl,—OC₅-C₁₈ heteroaryl, —NHC₁-C₁₈ alkyl; or —N(C₁-C₁₈ alkyl)₂;

R₂ and R₄ are each independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, orC₅-C₁₈ heteroaryl;

each R₇ or R₈ is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkenylene, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl,C₅-C₁₃ aryl, C₅-C₁₈ arylene, C₅-C₁₈ heteroaryl, or C₅-C₁₈ heteroarylene,wherein each of R₇ and R₈ may be optionally substituted;

X is O, NR_(A), or S(O)_(q);

R_(A) is C₁-C₆ alkyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈aryl, or C₅-C₁₈ heteroaryl; and q is 0-2.

In another embodiment, the invention provides a porous inorganic/organichomogenous copolymeric hybrid material, comprising an alkoxy silanemonomer and a heterocyclic silane monomer, wherein the alkoxy silanemonomer is selected from tetramethoxysilane, tetraethoxysilane,tetrapropoxysilane, and tetrabutoxysilane; and the heterocyclic silaneis selected from group consisting of

wherein

each R is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl,C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, C₆-C₁₈ aralkyl, C₆-C₁₈ heteroaralkyl, —Si(R^(c))₄,—C(O)R^(c), —C(S)R^(c), —C(NR)R^(c), —S(O)R^(c), —S(O)₂R^(c),—P(O)R^(c)R^(c), or —P(S)R^(c)R^(c);

each R^(c) is independently, H, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, —OC₁-C₁₈ alkyl; —OC₅-C₁₈ aryl; —OC₃-C₁₈ heterocycloalkyl,—OC₅-C₁₈ heteroaryl, —NHC₁-C₁₈ alkyl; or —N(C₁-C₁₈ alkyl)₂;

R₂ and R₄ are each independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, orC₅-C₁₈ heteroaryl;

each R₇ or R₈ is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkenylene, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl,C₅-C₁₈ aryl, C₅-C₁₈ arylene, C₅-C₁₈ heteroaryl, or C₅-C₁₈ heteroarylene,wherein each of R₇ and R₈ may be optionally substituted;

X is O, NR_(A), or S(O)_(q);

R_(A) is C₁-C₆ alkyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈aryl, or C₅-C₁₈ heteroaryl; and q is 0-2.

In another embodiment, the invention provides a porous inorganic/organichomogenous copolymeric hybrid material, comprising heterocyclic silanemonomers, wherein each heterocyclic silane monomer is independentlyselected from the group consisting of

wherein

each R is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl,C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, C₆-C₁₈ aralkyl, C₆-C₁₈ heteroaralkyl, —Si(R^(c))₄,—C(O)R^(c), —C(S)R^(c), —C(NR)R^(c), —S(O)R^(c), —S(O)₂R^(c),—P(O)R^(c)R^(c), or —P(S)R^(c)R^(c);

each R^(c) is independently, H, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, —OC₁-C₁₈ alkyl; —OC₅-C₁₈ aryl; —OC₃-C₁₈ heterocycloalkyl,—OC₅-C₁₈ heteroaryl, —NHC₁-C₁₈ alkyl; or —N(C₁-C₁₈ alkyl)₂;

R₂ and R₄ are each independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, orC₅-C₁₈ heteroaryl;

each R₇ or R₈ is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkenylene, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl,C₅-C₁₈ aryl, C₅-C₁₈ arylene, C₅-C₁₈ heteroaryl, or C₅-C₁₈ heteroarylene,wherein each of R₇ and R₈ may be optionally substituted;

X is O, NR_(A), or S(O)_(q);

R_(A) is C₁-C₆ alkyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈aryl, or C₅-C₁₈ heteroaryl; and q is 0-2.

In another embodiment, the invention provides a porous inorganic/organichomogenous copolymeric hybrid material, comprising analkenyl-functionalized silane monomer and a heterocyclic silane monomer,wherein the alkenyl-functionalized silane monomer is selected from thegroup consisting of methacryloxypropyltrimethoxysilane,methacryloxypropyltriethoxysilane, vinyltriethoxysilane,vinyltrimethoxysilane,N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane,(3-acryloxypropyl)trimethoxysilane,0-(methacryloxyethyl)-N-(triethoxysilylpropyl)urethane,N-(3-methacryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane,methacryloxymethyl triethoxysilane, methacryloxymethyltrimethoxysilane,methacryloxypropyl methyldiethoxysilane,methacryloxypropylmethyldimethoxysilane, methacryloxypropyltris(methoxyethoxy)silane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane hydrochloride,

wherein each R is independently H or a C₁-C₁₀ alkyl group and wherein R′is independently H or a C₁-C₁₀ alkyl group; and the heterocyclic silaneis selected from group consisting of:

wherein

each R is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl,C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, C₆-C₁₈ aralkyl, C₆-C₁₈ heteroaralkyl, —C(O)R^(c),—C(S)R^(c), —C(NR)R^(c), —S(O)R^(c), —S(O)₂R^(c), —P(O)R^(c)R^(c), or—P(S)R^(c)R^(c);

each R^(c) is independently, H, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, —OC₁-C₁₈ alkyl; —OC₅-C₁₈ aryl; —OC₃-C₁₈ heterocycloalkyl,—OC₅-C₁₈ heteroaryl, —NHC₁-C₁₈ alkyl; or —N(C₁-C₁₈ alkyl)₂;

R₂ and R₄ are each independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, orC₅-C₁₈ heteroaryl;

each R₇ or R₈ is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkenylene, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl,C₅-C₁₈ aryl, C₅-C₁₈ arylene, C₅-C₁₈ heteroaryl, or C₅-C₁₈ heteroarylene,wherein each of R₇ and R₈ may be optionally substituted;

X is O, NR_(A), or S(O)_(q);

R_(A) is C₁-C₆ alkyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈aryl, or C₅-C₁₈ heteroaryl; and q is 0-2.

In another embodiment, the invention provides a porous inorganic/organichomogenous copolymeric hybrid material, comprising an alkoxy silanemonomer and a heterocyclic silane monomer, wherein the alkoxy silanemonomer is selected from tetramethoxysilane, tetraethoxysilane,tetrapropoxysilane, and tetrabutoxysilane; and the heterocyclic silaneis selected from group consisting of

wherein

each R is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl,C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, C₆-C₁₈ aralkyl, C₆-C₁₈ heteroaralkyl, —Si(R^(c))₄,—C(O)R^(c), —C(S)R^(c), —C(NR)R^(c), —S(O)R^(c), —S(O)₂R^(c),—P(O)R^(c)R^(c), or —P(S)R^(c)R^(c);

each R^(c) is independently, H, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, —OC₁-C₁₈ alkyl; —OC₅-C₁₈ aryl; —OC₃-C₁₈ heterocycloalkyl,—OC₅-C₁₈ heteroaryl, —NHC₁-C₁₈ alkyl; or —N(C₁-C₁₈ alkyl)₂;

R₂ and R₄ are each independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, orC₅-C₁₈ heteroaryl;

each R₇ or R₈ is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkenylene, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl,C₅-C₁₈ aryl, C₅-C₁₈ arylene, C₅-C₁₈ heteroaryl, or C₅-C₁₈ heteroarylene,wherein each of R₇ and R₈ may be optionally substituted;

X is O, NR_(A), or S(O)_(q);

R_(A) is C₁-C₆ alkyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈aryl, or C₅-C₁₈ heteroaryl; and

q is 0-2.

In still another embodiment, the invention provides a porousinorganic/organic homogenous copolymeric hybrid material, comprisingheterocyclic silane monomers, wherein each heterocyclic silane monomeris independently selected from the group consisting of

wherein

each R is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl,C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, C₅-C₁₈ aralkyl, C₆-C₁₈ heteroaralkyl, —Si(R^(c))₄,—C(O)R^(c), —C(S)R^(c), —C(NR)R^(c), —S(O)R^(c), —S(O)₂R^(c),—P(O)R^(c)R^(c), or —P(S) R^(c)R^(c);

each R^(c) is independently, H, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, —OC₁-C₁₈ alkyl; —OC₅-C₁₈ aryl; —OC₃-C₁₈ heterocycloalkyl,—OC₅-C₁₈ heteroaryl, —NHC₁-C₁₈ alkyl; or —N(C₁-C₁₈ alkyl)₂;

R₂ and R₄ are each independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, orC₅-C₁₈ heteroaryl;

each R₇ or R₈ is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkenylene, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl,C₅-C₁₈ aryl, C₅-C₁₈ arylene, C₅-C₁₈ heteroaryl, or C₅-C₁₈ heteroarylene,wherein each of R₇ and R₈ may be optionally substituted;

X is O, NR_(A), or S(O)_(q);

R_(A) is C₁-C₆ alkyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈aryl, or C₅-C₁₈ heteroaryl; and q is 0-2.

Properties of the Hybrid Material

In certain embodiments, the invention provides a porousinorganic/organic homogenous copolymeric hybrid material, wherein thematerial consists essentially of spherical particles. In a furtherembodiment, the particles are approximately spherical.

In a further embodiment, the particles have an average diameter of about0.1 μm to about 300 μM. In a preferred embodiment, the particles have anaverage diameter of about 0.1 μm to about 60 μm. In another furtherembodiment, the particles have an average diameter of about 1 μm toabout 5 μm.

In one embodiment, the invention provides a material, wherein thematerial has a specific surface area of about 50-800 m²/g. In a furtherembodiment, the material has a specific surface area of about 100-700m²/g. In a preferred embodiment, the material has a specific surfacearea of about 100-300 m²/g.

In certain embodiments, the material of the invention has specific porevolumes of about 0.2 to 2.5 cm³/g. Preferred ranges of specific poresvolumes include from about 0.4 to 1.5 cm³/g.

Another embodiment of the invention includes a material of the inventionwherein the material has an average pore diameter of about 20 to 600 Å.In certain instances, the material has an average pore diameter of about50 to 300 Å. In preferred instances, the material has an average porediameter of about 75 to 125 Å.

In one embodiment, the invention provides a material of the invention,wherein the material is hydrolytically stable at a pH of about 1 toabout 14. In a further embodiment, the material is hydrolytically stableat a pH of about 10 to about 14. In a further embodiment, the materialis hydrolytically stable at a pH of about 12 to about 14. In anotherfurther embodiment, the material is hydrolytically stable at a pH ofabout 1 to about 5. In a further embodiment, the material ishydrolytically stable at a pH of about 1 to about 3.

Uses

The porous inorganic/organic homogenous copolymeric hybrid materials ofthe invention may be used as a liquid chromatography stationary phase; asequestering reagent; a solid support for combinatorial chemistry; asolid support for oligosaccharide, polypeptide, or oligonucleotidesynthesis; a solid support for a biological assay; a capillarybiological assay device for mass spectrometry; a template for acontrolled large pore polymer film; a capillary chromatographystationary phase; an electrokinetic pump packing material; a polymeradditive; a catalyst; or a packing material for a microchip separationdevice. In certain instances, the material comprises a HPLC stationaryphase. The materials of the invention are particularly suitable for useas a HPLC stationary phase or, in general, as a stationary phase in aseparations device, such as chromatographic columns, thin layer plates,filtration membranes, sample cleanup devices, and microtiter plates.

In one embodiment, the materials of the invention are used in aseparations device, wherein the device is selected from chromatographiccolumns, thin layer plates, filtration membranes, sample cleanupdevices, and microtiter plates. The materials and particles of theinvention have a wide variety of end uses in the separation sciences,such as packing materials for chromatographic columns (wherein suchcolumns may have improved stability to alkaline mobile phases andreduced peak tailing for basic analytes), thin layer chromatographic(TLC) plates, filtration membranes, microtiter plates, scavenger resins,solid phase organic synthesis supports (e.g., in automated peptide oroligonucleotide synthesizers), and the like having a stationary phasewhich includes porous inorganic/organic homogenous copolymeric hybridparticles. The stationary phase may be introduced by packing, coating,impregnation, etc., depending on the requirements of the particulardevice. In a particularly advantageous embodiment, the chromatographicdevice is a packed chromatographic column, such as commonly used inHPLC.

Preparation of Materials of the Invention

In one aspect, the invention provides a porous inorganic/organichomogenous copolymeric hybrid material comprising two or more repeatunits, wherein at least one repeat unit is an organosilane repeat unit D(previously described), prepared by the steps of (a) partiallycondensing an organic olefin, an alkenyl functionalized silane, analkoxysilane, or a heterocyclic silane, or mixtures thereof, (b) addinga heterocyclic silane, and (c) further reacting the heterocyclic silanewith the partially condensed polymer of step (a) to thereby prepare aporous inorganic/organic homogenous copolymeric hybrid materialcomprising a carbon-heteroatom-silicon functionality.

In another aspect, the invention provides a porous inorganic/organichomogenous copolymeric hybrid material comprising two or more repeatunits, wherein at least one repeat unit is an organosilane repeat unit D(previously described), prepared by the steps of (a) preparing apolyoligomeric siloxane (POS) by partial condensation oftetraalkoxylsilane C, (b) adding a heterocyclic silane, and (c) furtherreacting the heterocyclic silane with the POS to thereby prepare aporous inorganic/organic homogenous copolymeric hybrid materialcomprising a carbon-heteroatom-silicon functionality; wherein theheterocyclic silane is selected from the group consisting of

wherein

each R is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl,C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, C₆-C₁₈ aralkyl, C₆-C₁₈ heteroaralkyl, —Si(R^(c))₄, —C(O)R^(c), —C(S)R^(c), —C(NR)R^(c), —S(O)R^(c), —S(O)₂R^(c),—P(O)R^(c)R^(c), or —P(S)R^(c)R^(c);

each R^(c) is independently, H, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, —OC₁-C₁₈ alkyl; —OC₅-C₁₈ aryl; —OC₃-C₁₈ heterocycloalkyl,—OC₅-C₁₈ heteroaryl, —NHC₁-C₁₈ alkyl; or —N(C₁-C₁₈ alkyl)₂;

R₂ and R₄ are each independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, orC₅-C₁₈ heteroaryl;

each R₇ or R₈ is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkenylene, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl,C₅-C₁₈ aryl, C₅-C₁₈ arylene, C₅-C₁₈ heteroaryl, or C₅-C₁₈ heteroarylene,wherein each of R₇ and R₈ may be optionally substituted;

X is O, NR_(A), or S(O)_(q);

R_(A) is C₁-C₆ alkyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈aryl, or C₅-C₁₈ heteroaryl; and q is 0-2.

In one aspect, the invention provides a method of preparing a porousinorganic/organic homogenous copolymeric hybrid material comprising twoor more repeat units, wherein at least one repeat unit is anorganosilane repeat unit D (previously described), prepared by the stepsof

(a) partially condensing an organic olefin, an alkenyl functionalizedsilane, an alkoxysilane, or a heterocyclic silane, or mixtures thereof,(b) adding a heterocyclic silane, and (c) further reacting theheterocyclic silane with the partially condensed polymer of step (a) tothereby prepare a porous inorganic/organic homogenous copolymeric hybridmaterial comprising a carbon-heteroatom-silicon functionality.

In another aspect, the invention provides a method of preparing a porousinorganic/organic homogenous copolymeric hybrid material comprising twoor more repeat units, wherein at least one repeat unit is anorganosilane repeat unit D (previously described), prepared by the stepsof (a) preparing a polyoligomeric silaxane (POS) by partial condensationof tetraalkoxylsilane, (b) adding a heterocyclic silane, and (c) furtherreacting the heterocyclic silane with the POS to thereby prepare aporous inorganic/organic homogenous copolymeric hybrid material,comprising a carbon-heteroatom-silicon functionality.

In still another aspect, the invention provides a method of preparing aporous inorganic/organic homogenous copolymeric hybrid materialcomprising two or more repeat units, wherein at least one repeat unit isan organosilane repeat unit D (previously described), prepared by thesteps of (a) preparing a polyoligomeric silaxane (POS) by partialcondensation of tetraalkoxylsilane, (b) adding a heterocyclic silane,and (c) further reacting the heterocyclic silane with the POS to therebyprepare a porous inorganic/organic homogenous copolymeric hybridmaterial, comprising a carbon-heteroatom-silicon functionality; whereinthe heterocyclic silane is selected from the group consisting of

wherein

each R is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl,C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, C₆-C₁₈ aralkyl, C₆-C₁₈ heteroaralkyl, —Si(R^(c))₄, —C(O)R^(c), —C(S)R^(c), —C(NR)R^(c), —S(O) R^(c), —S(O)₂R^(c), —P(O)R^(c)R^(c), or —P(S)R^(c)R^(c);

each R^(c) is independently, H, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, —OC₁-C₁₈ alkyl; —OC₅-C₁₈ aryl; —OC₃-C₁₈ heterocycloalkyl,—OC₅-C₁₈ heteroaryl, —NHC₁-C₁₈ alkyl; or —N(C₁-C₁₈ alkyl)₂;

R₂ and R₄ are each independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, orC₅-C₁₈ heteroaryl;

each R₇ or R₈ is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkenylene, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl,C₅-C₁₈ aryl, C₅-C₁₈ arylene, C₅-C₁₈ heteroaryl, or C₅-C₁₈ heteroarylene,wherein each of R₇ and R₈ may be optionally substituted;

X is O, NR_(A), or S(O)_(q);

R_(A) is C₁-C₆ alkyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈aryl, or C₅-C₁₈ heteroaryl; and q is 0-2.

In yet another aspect, the invention provides a method of preparing aporous inorganic/organic homogenous copolymeric hybrid material offormula I:(A)_(w)(B)_(x)(C)_(y)(D)_(z);  (Formula I)wherein the order of repeat units A, B, C, and D may be random, block,or a combination of random and block; and wherein

A is an organic repeat unit which is covalently bonded to one or morerepeat units A, B, or D via an organic bond;

B is an organosiloxane repeat unit which is bonded to: one or morerepeat units A, B, or D via an organic bond; one or more repeat units B,C, or D via an inorganic bond; or one or more repeat unit D via acarbon-heteroatom-silicon bond;

C is an inorganic repeat unit which is bonded to: one or more repeatunits B, C, or 13 via an inorganic bond; or one or more repeat unit Dvia a carbon-heteroatom-silicon bond;

D is an organosilane repeat unit which is bonded to one or more repeatunits A, B, or D via an organic bond; bonded to one or more repeat unitsB, C, or D via an inorganic bond; or one or more repeat units B, C, or Dvia a carbon-heteroatom-silicon bond;

w, x, and y are positive numbers or zero; wherein w+x+y>0, z is apositive number;

the method comprising the steps of (a) partially condensing an organicolefin, an alkenyl functionalized silane, an alkoxysilane, or aheterocyclic silane, or mixtures thereof, (b) adding a heterocyclicsilane, and (c) further reacting the heterocyclic silane with thepartially condensed polymer of step (a) to thereby prepare a porousinorganic/organic homogenous copolymeric hybrid material comprising acarbon-heteroatom-silicon functionality.

In another aspect, the invention provides a method of preparing a porousinorganic/organic homogenous copolymeric hybrid material of formula II:(C)_(y)(D)_(z);  (Formula II)wherein the order of repeat units C and D may be random, block, or acombination of random and block; and wherein

C is an inorganic repeat unit which is bonded to: one or more repeatunits C or D via an inorganic bond; or one or more repeat units D via acarbon-heteroatom-silicon bond;

D is an organosilane repeat unit which is bonded to: one or more repeatunits C or D via an inorganic bond; one or more repeat units C or D viaa carbon-heteroatom-silicon bond; or one or more repeat units D via anorganic bond, and

y and z are positive numbers;

the method comprising the steps of (a) preparing a polyoligomericsilaxane (POS) by partial condensation of a tetraalkoxylsilane, (b)adding a heterocyclic silane, and (c) further reacting the heterocyclicsilane with the POS to thereby prepare a porous inorganic/organichomogenous copolymeric hybrid material, comprising acarbon-heteroatom-silicon functionality.

In one embodiment, the invention provides a method of synthesis whereinthe heterocyclic silane is selected from the group consisting of

wherein

each R is independently C₁-C₁₈; alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl,C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, C₆-C₁₈ aralkyl, C₆-C₁₈ heteroaralkyl, —Si(R^(c))₄,—C(O)R^(c), —C(S)R^(c), —C(NR)R^(c), —S(O)R^(c), —S(O)₂R^(c),—P(O)R^(c)R^(c), or —P(S)R^(c)R^(c);

each R^(c) is independently, H, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, —OC₁-C₁₈ alkyl; —OC₅-C₁₈ aryl; —OC₃-C₁₈ heterocycloalkyl,—OC₅-C₁₈ heteroaryl, —NHC₁-C₁₈ alkyl; or —N(C₁-C₁₈ alkyl)₂;

R₂ and R₄ are each independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, orC₅-C₁₈ heteroaryl;

each R₇ or R₈ is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkenylene, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl,C₅-C₁₅ aryl, C₅-C₁₈ arylene, C₅-C₁₈ heteroaryl, or C₅-C₁₈ heteroarylene,wherein each of R₇ and R₈ may be optionally substituted;

X is O, NR_(A), or S(O)_(q);

R_(A) is C₁-C₆ alkyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈aryl, or C₅-C₁₈ heteroaryl; and q is 0-2.

In another embodiment, the method steps (b) and (c) are performedcontemporaneously.

In still another embodiment, the hydrolytically condensing step is acid-or base-catalyzed. In a further embodiment, the condensation step isacid-catalyzed. In one embodiment, the acid is selected from the groupconsisting of hydrochloric acid, hydrobromic acid, hydrofluoric acid,hydroiodic acid, sulfuric acid, formic acid, acetic acid,trichloroacetic acid, trifluoroacetic acid, and phosphoric acid. Inanother further embodiment, the condensation step is base-catalyzed. Inanother embodiment, the base is selected from the group consisting ofammonium hydroxide, hydroxide salts of the group I and group II metals,carbonate and hydrogen carbonate salts of the group I metals, andalkoxide salts of the group I and group II metals.

In certain embodiments, method steps (a), (b), and (c) are performed inthe same reaction vessel.

In another embodiment, method steps (a) and (b) are performed in asolvent selected from the group consisting of water, methanol, ethanol,propanol, isopropanol, butanol, tert-butanol, pentanol, hexanol,cyclohexanol, hexafluoroisopropanol, cyclohexane, petroleum ethers,diethyl ether, dialkyl ethers, tetrahydrofuran, acetonitrile, ethylacetate, pentane, hexane, heptane, benzene, toluene, xylene,N,N-dimethylformamide, dimethyl sulfoxide, 1-methyl-2-pyrrolidinone,methylene chloride, chloroform, and combinations thereof.

In certain instances, the method step (a) or step (b) further comprisesthe step of addition of a porogen. In one embodiment, the porogen isselected from the group consisting of cyclohexanol, toluene,2-ethylhexanoic acid, dibutylphthalate, 1-methyl-2-pyrrolidinone,1-dodecanol, and Triton X-45.

In other instances, the method further comprises the step of adding afree radical polymerization initiator. In one embodiment, the freeradical polymerization initiator is selected from the group consistingof 2,2′-azobis-[2-(imidazolin-2-yl)propane]dihydrochloride,2,2′-azobisisobutyronitrile, 4,4′-azobis(4-cyanovaleric acid),1,1′-azobis(cyclohexanecarbonitrile),2,2′-azobis(2-propionamidine)dihydrochloride,2,2′azobis(2,4-dimethylpentanenitrile),2,2′-azobis(2-methylbutanenitrile), benzoyl peroxide,2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane,2,5-bis(tert-butylperoxy)butane,-2,5-dimethylhexane,2,5-bis(tert-butylperoxy)-2,5-dimethyl-hexyne,bis(1-(tert-butylperoxy)-1-methyethyl)benzene,1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butylhydroperoxide, tert-butyl peracetate, tert-butyl peroxide, tert-butylperoxybenzoate, tert-butylperoxy isopropyl carbonate, cumene peroxide,cyclohexanone hydroperoxide, dicumyl peroxide, lauroyl peroxide,2,4-pentanedione peroxide, peracetic acid, and potassium persulfate.

In other instances the method further comprises the step of heatingfollowing the addition of the free radical polymerization initiator.

In another embodiment, the method steps further comprise the step ofaddition of a surface modifier. In one embodiment, the surface modifieris selected from the group consisting of octyltrichlorosilane,octadecyltrichlorosilane, octyldimethylchlorosilane, and octadecyldimethylchlorosilane. In a further embodiment, the surface modifier isselected from octyltrichlorosilane and octadecyltrichlorosilane.Additionally, the methods of the invention may also include a step ofmodifying surfaces of the hybrid particles by formation of an organiccovalent bond between an organic group of the particle and a surfacemodifier. In this regard, the method may include a further step of byadding a surface modifier selected from the group consisting of anorganic group surface modifier, a silanol group surface modifier, apolymeric coating surface modifier, and combinations thereof. Likewise,the surface modifier may be a polymer coating, such as Sylgard®.

In one embodiment of the invention, the surface organic groups of thehybrid silica are derivatized or modified in a subsequent step viaformation of an organic covalent bond between the particle's organicgroup and the modifying reagent. Alternatively, the surface silanolgroups of the hybrid silica are derivatized into siloxane organicgroups, such as by reacting with an organotrihalosilane, e.g.,octadecyltrichlorosilane, or a halopolyorganosilane, e.g.,octadecyldimethylchlorosilane. Alternatively, the surface organic andsilanol groups of the hybrid silica are both derivatized. The surface ofthe thus-prepared material is then covered by the organic groups, e.g.,alkyl, embedded during the gelation and the organic groups added duringthe derivatization process or processes.

In yet another embodiment, the invention provides a method wherein saidparticles have been surface modified by a combination of organic groupand silanol group modification. In another embodiment, the particleshave been surface modified by a combination of organic groupmodification and coating with a polymer. In still another embodiment,the particles have been surface modified by a combination of silanolgroup modification and coating with a polymer. In other embodiments, theparticles have been surface modified via formation of an organiccovalent bond between the particle's organic group and the modifyingreagent. In another embodiment, the particles have been surface modifiedby a combination of organic group modification, silanol groupmodification, and coating with a polymer.

The method of the invention may also include a step of endcapping freesilanol groups according to methods which are readily known in the art.

In still another embodiment, the invention provides a method furthercomprising the step of adding a surfactant or stabilizer. In a furtherembodiment, the surfactant is Triton X-45, Triton X100, Triton X305,TLS, Pluronic F-87, Pluronic P-105, Pluronic P-123, sodiumdodecylsulfate (SDS), or Triton X-405.

In one embodiment, the pore structure of the as-prepared hybrid materialis modified by hydrothermal treatment, which enlarges the openings ofthe pores as well as the pore diameters, as confirmed by nitrogen (N₂)sorption analysis. The hydrothermal treatment is performed by preparinga slurry containing the as-prepared hybrid material and a solution oforganic base in water, heating the slurry in an autoclave at an elevatedtemperature, e.g., about 143 to 168° C., for a period of about 6 to 28h. The pH of the slurry can be adjusted to be in the range of about 8.0to 12.7 using tetraethylammonium hydroxide (TEAH) or TRIS andconcentrated acetic acid. The concentration of the slurry is in therange of about 1 g hybrid material per 5 to 10 mL of the base solution.

The thus-treated hybrid material is filtered, and washed with wateruntil the pH of the filtrate reaches about 7, washed with acetone ormethanol, then dried at about 100° C. under reduced pressure for about16 h. The resultant hybrid materials show average pore diameters in therange of about 100-300 Å. The surface of the hydrothermally treatedhybrid material may be modified in a similar fashion to that of thehybrid material that is not modified by hydrothermal treatment asdescribed in the present invention.

Moreover, the surface of the hydrothermally treated hybrid silicacontains organic groups, which can be derivatized by reacting with areagent that is reactive towards the hybrid materials' organic group.For example, vinyl groups on the material can be reacted with a varietyof olefin reactive reagents such as bromine (Br₂), hydrogen (H₂), freeradicals, propagating polymer radical centers, dienes, and the like. Inanother example, hydroxyl groups on the material can be reacted with avariety of alcohol reactive reagents such as isocyanates, carboxylicacids, carboxylic acid chlorides, and reactive organosilanes asdescribed below. Reactions of this type are well known in theliterature, see, e.g., March, J. “Advanced Organic Chemistry,” 3^(rd)Edition, Wiley, New York, 1985; Odian, G. “The Principles ofPolymerization,” 2^(nd) Edition, Wiley, New York, 1981.

In addition, the surface of the hydrothermally treated hybrid silicaalso contains silanol groups, which can be derivatized by reacting witha reactive organosilane. The surface derivatization of the hybrid silicais conducted according to standard methods, for example by reaction withoctadecyltrichlorosilane or octadecyldimethylchlorosilane in an organicsolvent under reflux conditions. An organic solvent such as toluene istypically used for this reaction. An organic base such as pyridine orimidazole is added to the reaction mixture to catalyze the reaction. Theproduct of this reaction is then washed with water, toluene and acetoneand dried at about 80° C. to 100° C. under reduced pressure for about 16h. The resultant hybrid silica can be further reacted with a short-chainsilane such as trimethylchlorosilane to endcap the remaining silanolgroups, by using a similar procedure described above.

The surface of the hybrid silica materials may also be surface modifiedby coating with a polymer. Polymer coatings are known in the literatureand may be provided generally by polymerization or polycondensation ofphysisorbed monomers onto the surface without chemical bonding of thepolymer layer to the support (type I), polymerization orpolycondensation of physisorbed monomers onto the surface with chemicalbonding of the polymer layer to the support (type II), immobilization ofphysisorbed prepolymers to the support (type III), and chemisorption ofpresynthesized polymers onto the surface of the support (type IV). See,e.g., Hanson et al., J. Chromat. A656 (1993) 369-380. As noted above,coating the hybrid material with a polymer may be used in conjunctionwith various surface modifications described in the invention. In apreferred embodiment, Sylgard® (Dow Corning, Midland, Mich., USA) isused as the polymer.

A stabilizer describes reagents which inhibit the coalescence ofdroplets of organic monomer and POS or PAS polymers in an aqueouscontinuous phase. These can include but are not limited to finelydivided insoluble organic or inorganic materials, electrolytes, andwater-soluble polymers. Typical stabilizers are methyl celluloses,gelatins, polyvinyl alcohols, salts of poly(methacrylic acid), andsurfactants. Surfactants (also referred to as emulsifiers or soaps) aremolecules which have segments of opposite polarity and solubilizingtendency, e.g., both hydrophilic and hydrophobic segments.

Because of their hybrid nature, the materials of the invention arestable over a broad pH range.

An advantageous feature of the materials of the invention is theirreduced swelling upon solvation with organic solvents than conventionalorganic LC resins. Therefore, in one embodiment, the material swells byless than about 25% (or 15% or 10% or even 5%) by volume upon solvationwith an organic solvent, such as acetonitrile, methanol, ethers (such asdiethyl ether), tetrahydrofuran, dichloromethane, chloroform, hexane,heptane, cyclohexane, ethyl acetate, benzene, or toluene.

The materials of the invention may be surface modified by formation ofan organic covalent chemical bond between an inorganic or organic groupof the material and a surface modifier. The surface modifier may be anorganic group surface modifier, a silanol group surface modifier, apolymeric coating surface modifier, or combinations thereof. Likewise,the surface modifier may be octyltrichlorosilane,octadecyltrichlorosilane, octyldimethyl chlorosilane, oroctadecyldimethylchlorosilane.

Additionally, the surface modifier is a combination of an organic groupsurface modifier and a silanol group surface modifier; a combination ofan organic group surface modifier and a polymeric coating surfacemodifier; a combination of a silanol group surface modifier and apolymeric coating surface modifier; or a combination of an organic groupsurface modifier, a silanol group surface modifier, and a polymericcoating surface modifier. The surface modifier may also be a silanolgroup surface modifier.

The inorganic portion of the hybrid monolith materials of the inventionmay be alumina, silica, titanium oxide, zirconium oxide, or ceramicmaterials.

In one embodiment, the invention provides a method of preparing thematerial of formula I, wherein the organic olefin monomer of A isselected from the group consisting of divinylbenzene, styrene, ethyleneglycol dimethacrylate, 1-vinyl-2-pyrrolidinone andtert-butylmethacrylate, acrylamide, methacrylamide,N,N′-(1,2-dihydroxyethylene)bisacrylamide, N,N′-ethylenebisacrylamide,N,N′-methylenebisacrylamide, butyl acrylate, ethyl acrylate, methylacrylate, 2-(acryloxy)-2-hydroxypropyl methacrylate,3-(acryloxy)-2-hydroxypropyl methacrylate, trimethylolpropanetriacrylate, trimethylolpropane ethoxylate triacrylate,tris[(2-acryloyloxy)ethyl]isocyanurate, acrylonitrile,methacrylonitrile, itaconic acid, methacrylic acid,trimethylsilylmethacrylate, N-[tris(hydroxymethyl)methyl]acrylamide,(3-acrylamidopropyl)trimethylammonium chloride,[3-(methacryloylamino)propyl]dimethyl(3-sulfopropyl)ammonium hydroxideinner salt,

In another embodiment, the invention provides a method of preparing thematerial of formula I, wherein the alkenyl-functionalized organosiloxanemonomer of B is selected from the group consisting ofmethacryloxypropyltrimethoxysilane, methacryloxypropyl triethoxysilane,vinyltriethoxysilane, vinyltrimethoxysilane,N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane,(3-acryloxypropyl)trimethoxysilane,O-(methacryloxyethyl)-N-(triethoxysilylpropyl)urethane,N-(3-methacryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane,methacryloxymethyltriethoxysilane, methacryloxy methyltrimethoxysilane,methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropyltris(methoxyethoxy)silane,3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilanehydrochloride,

wherein

each R is independently H or a C₁-C₁₀ alkyl group and wherein R′ isindependently H or a C₁-C₁₀ alkyl group. In a further embodiment, each Ris independently hydrogen, methyl, ethyl, or propyl. In another furtherembodiment, all of the R groups are identical and are selected from thegroup consisting of hydrogen, methyl, ethyl, or propyl.

In one embodiment, the invention provides a method of preparing amaterial of formula I or formula II, wherein the alkoxysilane monomer ofC is selected from the group consisting of tetramethoxysilane,tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

In certain instances, the tetraalkoxysilane is tetramethoxysilane ortetraethoxysilane.

In still another embodiment, the invention provides a method ofpreparing a material of formula I or formula II, wherein theheterocyclic silane monomer of D is selected from the group consistingof

wherein

each R is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl,C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, C₆-C₁₈ aralkyl, C₆-C₁₈ heteroaralkyl, —Si(R^(c))₄,—C(O)R^(c), —C(S)R^(c), —C(NR)R^(c), —S(O) R^(c), —S(O)₂R^(c),—P(O)R^(c)R^(c), or —P(S)R^(c)R^(c);

each R^(c) is independently, H, C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈heteroaryl, —OC₁-C₁₈ alkyl; —OC₅-C₁₈ aryl; —OC₃-C₁₈ heterocycloalkyl,—OC₅-C₁₈ heteroaryl, —NHC₁-C₁₈ alkyl; or —N(C₁-C₁₈ alkyl)₂;

R₂ and R₄ are each independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, orC₅-C₁₈ heteroaryl;

each R₇ or R₈ is independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₂-C₁₈alkenylene, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl,C₅-C₁₈ aryl, C₅-C₁₈ arylene, C₅-C₁₈ heteroaryl, or C₅-C₁₈ heteroarylene,wherein each of R₇ and R₈ may be optionally substituted;

X is O, NR_(A), or S(O)_(q);

R_(A) is C₁-C₆ alkyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈aryl, or C₅-C₁₈ heteroaryl; and q is 0-2.

The methods of the invention may also include a step of chemicallymodifying the organic olefin or alkenyl-functionalized organisiloxaneprior to copolymerization.

EXAMPLES

The present invention may be further illustrated by the followingnon-limiting examples describing the preparation of porousinorganic/organic hybrid materials, and their use.

Example 1

1,1-Dimethyl-1-Sila-2-Oxacyclohexane (DMSOH, Gelest Inc., Tullytown,N.J.), N-n-Butyl-AZA-2,2-dimethoxysilacyclopentane (BADMSP, Gelest Inc.,Tullytown, N.J.), or N-Methyl-AZA-2,2,4-trimethylsilacyclopentane(MATMSP, Gelest Inc., Tullytown, N.J.) was added to a polyethoxylatedsiloxane polymer (POS, as described in K. Unger, et. al. Colloid &Polymer Science vol. 253 pp. 658-664 (1975)) in a flask. The resultingmixture was agitated at 25-120° C. for 0.08-24 hours under a nitrogenatmosphere. The resulting polyorganoalkoxysiloxanes were colorless tocolored viscous liquids. The chemical formulas are listed in Table 1 forthe organotrialkoxysilanes and alkoxysilanes used to make the productpolyorganoalkoxysiloxanes (POS). Specific amounts are listed in Table 2for the starting materials used to prepare these products. Viscosity wasdetermined for these materials using a Brookfield digital viscometerModel DV-II (Middleboro, Mass.).

TABLE 1 Organoalkoxysilanes POS Product Organoalkoxysilanes ChemicalStructure Chemical Formula 1a, b, c, d, e 1,1-Dimethyl-1-Sila-2-Oxacyclohexane (DMSOH)

Si(OH)_(x)(OCH₂CH₃)_(y)(O—)_(z) 1f, g N-n-Butyl-AZA-2,2-dimethoxysilacyclo Pentane (BADMSP)

Si(OH)_(x)(OCH₂CH₃)_(y)(O—)_(z) 1h, i, j N-Methyl-AZA-2,2,4-trimethylsilacyclo- pentane (MATMSP)

Si(OH)_(x)(OCH₂CH₃)_(y)(O—)_(z)

TABLE 2 Organotrialkoxysilane POS Conditions Viscosity Product (g) (g)(° C., h) (cP) 1a 5.8 58 25° C., 5 min — 1b 5.8 58 120° C., 23 h 170 1c5.8 58 100° C., 4 h 47 1d 10.6 53 100° C., 21 h 119 1e 53 265 120° C.,16 h 26 1f 5.8 58 25° C., 5 mm — 1g 5.8 58 120° C., 18 h 541 1h 5.8 58100° C., 4 h 1180 1i 5.8 58 100° C., 2 h 511 1j 10.6 53 100° C., 2 h 26

Example 2

A mixture of Triton® X-100 (Dow Chemical, Midland, Mich.), ethanol(anhydrous, J. T. Baker, Phillipsburgh, N.J.), and deionized water washeated at 55° C. for 0.5 h. Using a rotor/stator mixer (Model 100 L,Charles Ross & Son Co., Hauppauge, N.Y.), a organosiloxane/POS mixturefrom example 1 was emulsified in the ethanol/water/triton mixture.Thereafter, 14.8 M ammonium hydroxide (NH₄OH; J. T. Baker,Phillipsburgh, N.J.) was added into the emulsion to gel the emulsionbeads. Suspended in the solution, the gelled product was transferred toa flask and stirred at 55° C. for 16 h. Thereafter, the emulsion wasagitated mechanically at 80° C. for 16-24 hours. Upon cooling, thesuspension of formed particles was filtered and then washedconsecutively with copious amounts of methanol HPLC grade, J. T. Baker,Phillipsburgh, N.J.), water and then methanol. The particles were thendried at 80° C. at a reduced pressure for 16 hours. Specific amounts ofstarting materials used to prepare these products are listed in Table 3.The specific surface areas (SSA), specific pore volumes (SPV) and theaverage pore diameters (APD) of these materials were measured using themulti-point N₂ sorption method and are listed in Table 3 (MicromeriticsASAP 2400; Micromeritics Instruments Inc., Norcross, Ga., orequivalent). The specific surface area was calculated using the BETmethod, the specific pore volume was the single point value determinedfor P/P₀>0.98, and the average pore diameter was calculated from thedesorption leg of the isotherm using the BJH method. The % C, % H, % N fthese materials were measured by combustion analysis (CE-440 ElementalAnalyzer; Exeter Analytical Inc., North Chelmsford, Mass., orequivalent).

TABLE 3 Triton POS POS X100 EtOH H₂O NH₄OH SSA SPV APD Product Reagent(g) (g) (g) (g) (mL) % C % H % N (m²/g) (cm³/g) (Å) 2a 1a 63.8 5.6 52280 44 2.39 0.96 0.06 319 0.64 77 2b 1b 63.8 5.6 52 280 44 3.50 1.160.00 431 0.82 68 2c 1c 63.8 5.6 52 280 44 1.62 0.95 0.00 327 0.64 78 2d1d 63.6 5.6 52 280 44 7.11 2.03 0.00 511 0.82 51 2e 1e 286.2 25.2 2341260 198 5.54 1.80 0.05 460 0.69 49 2f 1f 63.8 5.6 52 280 44 7.29 1.790.98 366 0.56 57 2g 1g 63.8 5.6 52 280 44 6.96 1.82 0.86 396 0.51 49 2h1h 63.8 5.6 52 280 44 8.55 2.52 1.26 376 0.40 42 2i 1i 63.8 5.6 52 28044 8.06 2.78 1.22 437 0.41 38 2j 1j 63.6 5.6 52 280 44 12.63 3.46 1.92344 0.33 42

Example 3

Spherical, porous, hybrid inorganic/organic particles of Examples 2 weremixed with 0.1 M tris(hydroxymethyl)aminomethane (TRIS, AldrichChemical, Milwaukee, Wis.) aqueous solution, yielding a 16% by weightslurry. The resultant slurry was then enclosed in a stainless steelautoclave and heated to between 145° C. for 20 hours. After theautoclave cooled to room temperature the product was filtered and washedrepeatedly using water and methanol (HPLC grade, J. T. Baker,Phillipsburgh, N.J.), and then dried at 80° C. under vacuum for 16hours. Specific hydrothermal conditions are listed in Table 4 (mL ofbase solution/gram of hybrid silica particle, concentration and pH ofinitial TRIS solution, reaction temperature). The specific surface areas(SSA), specific pore volumes (SPV), the average pore diameters (APD) andthe % C of these materials are listed in Table 4 and were measured asdescribed in Examples 2.

TABLE 4 Loss in SSA SPV APD SSA MPA % Product Precursor pH % C % N(m²/g) (cc/g) (Å) (m²/g) (m²/g) μp 3a 2c 9.53 0.15 0.00 90 0.56 230 23719 21 3b 2d 9.57 3.57 0.00 211 0.95 152 300 13  6 3c 2e 9.43 3.17 0.00199 0.72 129 261 18  9 3d 2g 9.60 6.28 0.93 89 0.40 140 307 15 17 3e 2i9.51 5.87 0.83 42 0.24 167 395 7 17 3f 2j 9.71 8.34 1.17 47 0.26 167 2979 19

Example 4

The particles of hybrid materials prepared according to Examples 3c wereseparated by particle size into 4.4 and 11.7 μm fractions (Table 5,entries 4a and 4b). The surface of these materials fraction weremodified with chlorodimethyloctadecylsilane (CDMO, Aldrich Chemical,Milwaukee, Wis.), using imidazole (Aldrich Chemical, Milwaukee, Wis.) inrefluxing toluene (110° C., 4 hours). The reaction was then cooled andthe product was filtered and were washed successively with water,toluene, 1:1 v/v acetone/water, and acetone (all solvents from J. T.Baker), and then dried at 80° C. under reduced pressure for 16 hours.Reaction data is listed in Table 6 and were measured as described inExamples 2. The surface concentration of octadecylsilyl groups wasdetermined to be 3.2-3.4 μmol/m² by the difference in particle % Cbefore and after the surface modification as measured by elementalanalysis.

TABLE 5 dp₅₀ Unsized vol % 90/10 SSA SPV APD Product Precursor (μm)ratio % C (m²/g) (cc/g) (Å) MPA (m²/g) % μP 4a 3c 4.37 1.47 0.75 2360.68 114 49 21 4b 3c 11.66 1.70 1.88 219 0.90 156 36 16

TABLE 6 C₁₈ Imidazole Toluene Coverage Product Precursor Hybrid (g) CDMO(g) (g) (mL) % C (μmol/m²) 5a 4a 3.5 2.87 0.67 17.5 15.2 3.17 5b 4b 4836.5 8.59 240 15.9 3.37

Example 5

The surface of C₁₈-bonded hybrid materials 5a and 5b were furthermodified with trimethylchlorosilane (TMCS, Aldrich Chemical, Milwaukee,Wis.), using imidazole (Aldrich Chemical, Milwaukee, Wis.) in refluxingtoluene (110° C., 4 hours). The reaction was then cooled and the productwas filtered and were washed successively with water, toluene, 1:1 v/vacetone/water, and acetone (all solvents from J. T. Baker), and thendried at 80° C. under reduced pressure for 16 hours. Reaction data islisted in Table 7 and were measured as described in Examples 2.

TABLE 7 Hybrid TMSC Imidazole Toluene Product Precursor (g) (g) (g) (mL)% C 6a 5a 4.0 1.03 0.77 20.0 15.38 6b 5b 55 13.1 9.84 275 16.03

Example 6

Following the method described in U.S. Pat. No. 6,686,035, one or moreorganoalkoxysilanes alone or in combination with a one or morealkoxysilanes (all from Gelest Inc., Tullytown, Pa.) listed Table 8below are mixed with an alcohol (HPLC grade, J. T. Baker, Phillipsburgh,N.J.) and 0.1 N hydrochloric acid (Aldrich Chemical, Milwaukee, Wis.) ina flask. The resulting solution is agitated and refluxed for 16 h in anatmosphere of argon or nitrogen. Alcohol is removed from the flask viadistillation at atmospheric pressure. Residual alcohol and volatilespecies are removed by heating at 115-140° C. for 1-2 h in a sweepingstream of argon or nitrogen or by heating at 125° C. under reducedpressure for 1-2 h. The resulting polyorganoalkoxysiloxanes (POS) arecolorless viscous liquids.

TABLE 8 Organoalkoxysilanes Alkoxysilane Chemical Formula ChemicalFormula H₂C═C(CH₃)CO₂C₃H₆Si(OCH₃)₃, Si(OCH₃)₄,H₂C═CHC₆H₄(CH₂)₂Si(OCH₃)₃, Si(OCH₂CH₃)₄ H₂C═CHSi(OCH₂CH₃)₃,CH₃Si(OCH₂CH₃)₃. C₂H₅Si(OCH₂CH₃)₃, C₆H₅Si(OCH₂CH₃)₃,(CH₃CH₂O)₃Si(CH₂)₂Si(OCH₂CH₃)₃

Example 7

1,1-Dimethyl-1-Sila-2-Oxacyclohexane (DMSOH, Gelest Inc., Tullytown,N.J.), N-n-Butyl-AZA-2,2-dimethoxysilacyclopentane (BADMSP, Gelest Inc.,Tullytown, N.J.), or N-Methyl-AZA-2,2,4-trimethylsilacyclopentane(MATMSP, Gelest Inc., Tullytown, N.J.) are added to a methacryloxypropylor vinyl containing POS selected from Example 6, in a flask and isagitated at 25-120° C. for 24 hours under a nitrogen atmosphere. Thisproduct is then mixed under a nitrogen purge at ambient temperature for0.5 hours with divinylbenzene (DVB; 80%; Dow Chemical, Midland, Mich.;washed 3× in 0.1 N NaOH, 3× in water, and then dried MgSO₄ from AldrichChemical), 2,2′-azobisisobutyronitrile (AIBN; 98%, Aldrich Chemical),and one or more of the following reagents: toluene (HPLC grade, J. T.Baker, Phillipsburgh, N.J.), cyclohexanol (CXL; Aldrich, Milwaukee,Wis.), dibutylphthalate (DBP; Sigma; Milwaukee, Wis.), Triton® X-45 (OilX-45; Fluka, Milwaukee, Wis.). In a separate flask, a solution ofTriton® X-45 (Aq X-45; Fluka, Milwaukee, Wis.) or Triton® X-100 (AqX-100; Fluka, Milwaukee, Wis.) and tris(hydroxymethyl)aminomethanelauryl sulfate (TDS; Fluka, Milwaukee, Wis.) in water and ethanol isprepared by mixing and heating to 60° C. for 0.5-1.0 hours. The twosolutions are combined and then emulsified using a rotor/stator mixer(Model 100L, Charles Ross & Son Co., Hauppauge, N.Y.) for 4 minutesunder an argon flow. Next, a solution of 14.8 M ammonium hydroxide(NH₄OH; J. T. Baker, Phillipsburgh, N.J.) is added to the emulsion overa minute, and the emulsification continues for 20 minutes. Thereafter,the emulsion is agitated mechanically at 80° C. for 16-24 hours. Uponcooling, the suspension of formed particles is filtered and is thenwashed consecutively with copious amounts of methanol, water and thenmethanol.

INCORPORATION BY REFERENCE

The entire contents of all patents, published patent applications andother references cited herein are hereby expressly incorporated hereinin their entireties by reference.

EQUIVALENTS

Those skilled in the art will recognize, or be able to ascertain usingno more than routine experimentation, numerous equivalents to thespecific procedures described herein. Such equivalents are considered tobe within the scope of this invention and are covered by the followingclaims.

What is claimed is:
 1. A method of preparing a porous inorganic/organichomogenous copolymeric hybrid material, comprising two or more repeatunits, wherein at least one repeat unit is an organosilane repeat unitD, and wherein the material has the formula(A)_(w)(B)_(x)(C)_(y)(D)_(z) wherein the order of repeat units A, B, C,and D may be random, block, or a combination of random and block andwherein: A is an organic repeat unit which is covalently bonded to oneor more repeat units A, B, or D via an organic bond; B is anorganosiloxane repeat unit which is bonded to: one or more repeat unitsA, B, or D via an organic bond; one or more repeat units B, C, or D viaan inorganic bond; or one or more repeat units D via acarbon-heteroatom-silicon bond; C is an inorganic repeat unit which isbonded to: one or more repeat units B, C, or D via an inorganic bond; orone or more repeat units D via a carbon-heteroatom-silicon bond; D is anorganosilane repeat unit and is bonded to: one or more repeat units A,B, or D via an organic bond; one or more repeat units B, C, or D via aninorganic bond; or one or more repeat units B, C, or D via acarbon-heteroatom-silicon bond; w, x, and y are each independentlypositive numbers or zero, wherein w+x+y>0; and z is a positive number;wherein A is selected from the group consisting of

wherein each R is independently H or a C₁-C₁₀ alkyl group; k is aninteger from 3-6; m is an integer of from 1 to 20; n is an integer offrom 0 to 10; and Q is hydrogen, N(C₁₋₆alkyl)₃,N(C₁₋₆alkyl)₂(C₁₋₆alkylene-SO₃), or C(C₁₋₆hydroxy alkyl)₃; wherein B isselected from the group consisting of

wherein C is

and wherein repeat unit D is selected from the group consisting of

wherein R₂ and R₄ are each independently C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl,C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl,or C₅-C₁₈ heteroaryl; each R₇ or R₈ is independently C₁-C₁₈ alkyl,C₂-C₁₈ alkenyl, C₂-C₁₈ alkenylene, C₂-C₁₈ alkynyl, C₃-C₁₈ cycloalkyl,C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, C₅-C₁₈ arylene, C₅-C₁₈ heteroaryl,or C₅-C₁₈ heteroarylene, wherein each of R₇ and R₈ may be optionallysubstituted; X is O, NR_(A), or S(O)_(q); R_(A) is C₁-C₆ alkyl, C₂-C₁₈alkenyl, C₃-C₁₈ cycloalkyl, C₃-C₁₈ heterocycloalkyl, C₅-C₁₈ aryl, orC₅-C₁₈ heteroaryl; and q is 0-2; comprising the steps of (a) partiallycondensing an organic olefin, an alkenyl functionalized silane, analkoxysilane, or a heterocyclic silane, or mixtures thereof, (b) addinga heterocyclic silane, and (c) further reacting the heterocyclic silanewith the partially condensed polymer of step (a) to thereby prepare aporous inorganic/organic homogenous copolymeric hybrid materialcomprising a carbon-heteroatom-silicon functionality.
 2. The method ofclaim 1, wherein step (a) or step (b) further comprises the step ofaddition of a porogen.
 3. The method of claim 1, further comprising thestep of surface modifying the material, wherein said surface modifier isselected from the group consisting of octyltrichlorosilane,octadecyltrichlorosilane, octyldimethylchlorosilane, andoctadecyldimethylchloro silane.
 4. The method of claim 1, furthercomprising the step of endcapping free silanol groups.